Method for the control of undesirable vegetation with 3, 5, 6-substituted uracils



United States Patent 3 374 083 METHOD FOR THE C(lNTROL OF UNDESIR- ABLE VEGETATION WITH 3,5,6-SUBSTITUTED URACILS Harvey M. Loux, Hockessin, De]., assignor to E. I. du

R is alkyl of 1 through 10 carbon atoms, substituted alkyl of 1 through 8 carbon atoms, aryl of through 10 carbon atoms, substituted phenyl, aralkyl of 5 through 13 carbon atoms, substituted aralkyl of 5 through 13 carbon atoms, alkenyl of 3 through 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, cycloalkenyl of 4 through 12 carbon atoms, cycloalkyl alkyl of 4 through 13 carbon where atoms, cycloalkenyl :alkyl of 5 through 13 carbon atoms, (substituted cycloalkyDalkyl of 5 through 14 carbon atoms, and (substituted cyc1oalkenyl)alkyl of r 5 through 14 carbon atoms;

R is chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, nitro, alkoxymethyl of 2 through 6 carbon atoms, hydroxy alkyl of 1 through 2 carbon atoms, alkylthio containing'l through 4 carbon atoms, bromomethyl, fluoroet-hyl, or chloromethyl; or in the case where R is a cycloalkyl radical containing 3 through 7 carbon atoms, R may be hydrogen; and l 7 R is cycloalkyl of 3 through 7 carbon atoms, alkenyl of 3 through 5 carbon atoms, alkylthio of 1 through 4 'carbon atoms, alkyl'thiomethyl of 2 through 3 carbon atoms or alkoxymethyl of 2 through '5 carbon atoms.

a The salts of thesecompounds can also be used accord ice standing that it is representative only, and is not intended to illustrate actual structure:

where:

R, R and R are defined as in Formula 1, and

NB is a nitrogenous base having an ionization constant K of 210 in water.

polyamines, arylamines, or heterocyclicamines. Illustrative of such amines are:

sec-butylamine 2-amino-2-methyl-1,3-propanediol trimethylenediamine ethanolamine dodecylamine ethylenediamine hexamethylenediamine cocoadiamine tallowdiamine hexamethyleneimine cyclohexylamine methoxypropylamine methylamine dimethylamine trimethylamine ammonia ethylamine propylamine butylamine octylamine pyridine piperidine tetramethylguanidine acetamidine benzylamine diethylenediamine Z-aminobutanol-l Z-aminooctanol-l tuted phenols. These complexes have the formula where R, R and R are defined as in Formula 1, X is hydrogen, chlorine, nitro, alkyl of 1 through 3 carbon atoms, bromine or OR where R is alkyl' of 1 through 3 carbon atoms, 1 Y is chlorine or alkyl of 1 through 3 carbon atoms, m is a number 1 through 5, and n is 1 or 2.

, The amine addition compounds and phenol complexes of Formulate 2 and 3 above are novel compounds and provide formulation advantages such as increased water 3 solubility and increased oil solubility over the uracils themselves Their herbicidal effectiveness, however, is primarily due to their uracil content.

Preferred for use according to this invention are comwhere:

R is alkyl of 2 through 8 carbon atoms, substituted alkyl of '2 through 8 carbon atoms, phenyl, substituted phenyl, aralkyl of 6 through 10 carbon atoms, substituted aralkyl of 6 through 10 carbon atoms, cycloalkyl of 3 through 8 carbon atoms, cy-cloalkenyl of 5 through 8 carbon atoms, cycloalkyl alkyl of 4 through 9 carbon atoms, or (substituted cycloalkyl)alkyl of 5 through 14 carbon atoms; 7

R is chlorine, bromine, iodine, methyl, hydroxymethyl,

methoxymethyl or nitro; and

R is alkoxymethyl of 2 through 3 carbon atoms, cycloalkyl of 3 through 6 carbon atoms or alkenyl of 3 through 4 carbon atoms.

In Formulae 1, 2, 3, and 4 the term substituted alkyl is intended to include such radicals as bromoalkyl of 1 through 10 carbon atoms,

chloroalkyl of 1 through 10 carbon atoms,

hydroxyalkyl of 1 through 8 carbon atoms,

alkoxyalkyl of 2 through 8 carbon atoms,

alkoxy carbonyl alkyl of 3 through 8 carbon atoms, and cyanoalkyl of 2 through 8 carbon atoms.

Similarly, the terms aryl and substituted phenyl embrace radicals such as The terms aralky and substituted aralkyl are intended to include such radicals as furfuryl, Y

benzyl, a 1

phenylalkyl of Sjthrough 11 carbon atoms (total), chlorobenzyl, dichlorobenzyl,

alkylbenzyl of 8 through 11 carbon atoms (total), dialkylbenzyl of 9 through 13 carbon atoms (total), nitrobenzyl,

alkoxybenzyl of 8 through 11 carbon atoms (total), and naphthylmethyl,

The terms cycloalkyl, cycloalkenyl, cycloalkyl alkyl, and cycloalkenyl alkyl will include cyclohexyl,

cyclohexenyl,

cyclohexylalkyl,

cyclohexenylalkyl,

cyclopentyl,

cyclopentenyl,

cyclopentylalkyl,

cyclopentenylalkyl,

norbornyl,

norbornenyl,

norbornylalkyl,

norbornenylalkyl,

bicyclo(2,2,2)octyl,

bicyclo (2,2,2) octenyl,

bieyclo (2,2,2) octylalkyl, bicyclo(2,2,2)octenylalkyl, cyclopropyl,

cyclobutyl,

cyclobutylalkyl,

cyclobutenyl,

cyclobutenylakyl,

hexahydroindanyl,

tetrahydroindanyl,

hexahydroindenyl,

hexahydroindenyl alkyl, tetrahydroindanyl alkyl, hexahydroindanyl alkyl, hexahydro-4,7-methanoindenyl, tetrahydro-4,7-methanoindanyl, hexahydro-4,7-methanoindanyl, hexahydro-4,7-methanoindenyl alkyl, tetrahydro-4,7-methanoindanyl alkyl, hexahydro-4,7-methanoindanyl alkyl, decahydronaphthyl, decahydronaphthyl alkyl, tetrahydronaphthyl, tetrahydronaphthyl alkyl, decahydro-1,4-methanonaphthyl, decahydro-1,4-methanonaphthyl alkyl, octahydro-l,4-methanonaphthyl, octahydro-l,4-methanonaphthyl alkyl, decahydro-1,4,5,8-dimethanonaphthyl, decahydro-1,4,5,8-dimethanonaphthyl alkyl, octahydro-1,4,S,8-dimethanonaphthyl, and octahydro-1,4,5,8-dimethanonaphthyl alkyl.

These cyclic substituents can be further substituted with alkyl groups of '1 through 4 carbon atoms, methoxy, chlorine and bromine.

In the process of combining the various 3,5,6-substituents described above for R, R and R it is surprising to find that strikingly similar herbicidal activity can be obtained with seemingly unrelated substituents. On the other hand, it is equally surprising to find useful selective phytotoxicity (applicable in certain crop areas) when a relatively minor structural modification for R (for example a normal alkyl chain altered to a branched chain) is made. Each S-substituent (described for R above) for example, has a maximum and minimum range of herbicidal effectiveness and/ or specie selectivity dependent on the nature of the substituent in the 3- or 6-position. There is little continuity of herbicidal effect which can be ascribed to a particular substituent independently of the other two substituents in the 3,5,6-positions.

UTILITY that they exert their action against both broadleaf and.

grass weeds, are effective against hard-to-kill nutsedge and perennial grasses such as quack grass, Johnson grass,

and Bermuda grass, and are effective on highly adsorptive.

industrial areas, railroad, rights-of-way, and areas adja-,

cent to croplands in agricultural areas.

Certain of the uracils also exhibit selective herbicidal action in crops. By properly selecting a uracil of the invention and a rate and time of application, annual grass and broadleaf seedlings in such crops as asparagus, corn, flax, sugar cane, pineapple, safflower, peanuts, citrus, alfalfa, strawberries, gladiolus, stone fruits and cucurbits can be controlled.

By proper selection of rate and time of application, certain of the uracils can also be used to control Weeds growing in dormant crops.

This selective activity and activity on weeds growing in dormant crops is described in more detail in the examples.

The precise amounts of uracils to be used in any given situation will, of course, vary according to the particular end result desired, the use involved, the plant and soil involved, the formulation used, the mode of application, prevailing weather conditions, foliage density and like factors. Since so many variables play a role, it is not possible to indicate a rate of application suitable for all situations. Broadly speaking, the compounds are used at levels of about A pound per acre to about 25 pounds per acre. For selective weed control in crops, rates of A to 8 pounds per acre will generally be used. More of the active material can be used to control difiicult-to-kill species growing under adverse conditions. Economic factors, such as inaccessibility of the area to be treated, e.g., fire breaks in forests, may also favor higher rates, with less frequent treatments.

In some situations it is desirable that the active uracil herbicide be released slowly from the carrier. Such compositions are particularly useful for application to gravel and cinder drive-ways and the like, where they release their herbicidal ingredients slowly over a long period of time and thus eliminate the necessity for frequent application.

Such compositions are made by incorporating the uracil into a solid or semi-solid matrix of a material such as Portland cement or calcium sulfate. The uracils will be present in these compositions in varying concentrations depending upon the ultimate use of the products. Generally, they will contain form 1% to 40%, by weight, of uracil. They can be prepared by any of the well-known techniques, such as granulating or pelletizing.

Herbicidal formulations can also be prepared containing a fungicide or bactericide. When such compositions are applied to the soil, the fungicidal or bactericidal ingredients retard the breakdown of the uracils by soil microorganisms and thus renders them stable over a longer period of time. The fungicides and bactericides which can be incorporated into these compositions can be any of the well-known products such as, for example, antibiotics such as penicillin, phenols, thio carbamates, and the like. The amount of microbiocide to be included in such compositions will naturally vary with their ultimate use. Generally, however, they will contain from 1% to 70% of a microbiocide.

The uracils of this invention can also be incorporated into paints, particularly marine paints, for application to surfaces where the growth of plants such as algae is undesirable. Such compositions are prepared by dissolving or suspending the uracil in a paint-compatible solvent. Uracils will be present in such compositions at concentra tions of from 1% to 10%.

The uracils of this invention can also be dissolved in a suitable solvent or dispersed in a suitable carrier and impregnated into wooden objects such as construction timbers or railroad ties. When these objects are placed in or near the ground, the uracils slowly leach from them,

thus preventing the growth of weeds in the nearby areas. Such wooden objects, can also be floated on the surface of water in which undesirable aquatic growth is present.

Again, the uracil is slowly leached from the wood and prevents growth of nearby aquatic weeds and algae for extended periods.

The concentration of uracil to be impregnated into any such wooden object will vary according to the nature of the wood and the type of weed to be controlled.

PREPARATION OF THE COMPOUNDS Those uracils of Formula 1 where R is alkyl, or alkenyl, as well as the uracil starting reactants for the reactions of Equations 10 to 12, can be prepared by methods heretofore described in the literature. For example, one method for the preparation of these compounds is illus trated by the following equations:

For more general details, note the publication by Behrend and Myer in Ann., 314, 219 (1901) and also Ber., 33, 622 (1900).

In the method of Equations 5 and 6, the esters of 13- amino-a,fi-unsaturated acids are first prepared by reacting the corresponding ,B-keto esters with aqueous ammonia [Conrad and Epstein, Ber., 20, 3054 (1887)]. These properly substituted B-amino-u,fl-unsaturated esters are then reacted with an isocyanate in an inert solvent such as toluene or xylene, and heated for a short interval of time at reflux temperature.

The reaction mixture is chilled, filtered, and the filtrate distilled to remove the solvent. Generally, a viscous liquid residue remains which is crude 3-(3-substituted-ureido)- a e-unsaturated ester. This can be reacted without further purification with an aqueous alcoholic alkaline solution at reflux temperature to bring about the desired uracil ring closure. At this point, the reaction is made slightly acidic with a strong acid such as hydrochloric acid and distilled to remove the alcohol. After the remaining aqueous solution has, been chilled, the corresponding substituted uracil separates as'an essentially pure solid.

Another method for preparing the uracil starting reactants is illustrated by the following equations:

ol l According to Equations 7 and 8, an appropriately substituted urea is reacted with a B-keto ester or an a-substituted fl-keto ester substituted with such radicals as alkoxy, fluorine, alkyl, or alkeny-l, and an acid catalyst, at reflux in a solvent from which water is removed continuously. After the water has all been removed, the solution is stripped and taken up in ethanolcon'taining a base such as sodium methoxide. After a few minutes reflux, the solvent is removed, and the residual oil taken up in water and acidified, whereupon the desired product separates in crystalline form.

The product formed at the end of the first step, i.e., after the water has been removed, is a ureido compound of the type referred to in Equation 7. It can be isolated and purified if desired; however, this is not necessary or advantageous.

These ureido compounds referred to above are believed to exist in either or both of two tautomeric forms, as illustrated inthe following equation:

The uracils which are substituted in the 5-position with halogen, nitro, chl'oromethyl and hydroxyme'thyl groups can be prepared by an extrapolation of methods heretofore described in the literature for related compounds.

' For example, the preparation of those compounds having a halogen su'bstituent in the 5-position is illustrated by Equation 10. For more general details, see J. Amer. Chem. Soc., 61, 1015 (1939); Ann, 305, 314; Ann., 352,

The S-nitro uracils are prepared by direct nitration of uracils having no substituent in the 5-position, as illustrated in Equation 11. For a description of this method, see I. Am. Chem. Soc., 30, 1156 (1908).

I ll I l l O= CH--CH: O= GIL-CH2 N I l N H (1H2 CH2 H CH2 CH:

GET-CH2 CHz-CHr The reaction. of formaldehyde with uracils not substituted in the 5-position gives uracils substituted in the 5- position with a hydroxymethyl group, as illustrated by Equation 12. For greater detail see Gazz. Chim. Ital., 79, 447 (1949).

Thes S-hydroxymethyl uracils can be easily reacted with alcohols, or thionylchloride, to give corresponding S-alkoxymethyl, and S-chloromethyl uracils.

The salts of the compounds of Formula 1 are prepared by conventional methods such as dissolving the free uracil in an aqueous or nonaqueous solution of at least an equimolar amount of a base or basic salt containing the desired cation. For example, a sodium salt can be prepared by dissolving the uracil in water containing an equimolar amount of sodium hydroxide. The salt can then be isolated from the solution by removal of the water. The uracil salts which are not soluble in water can be prepared by treating an aqueous solution of an alkali metal salt of the uracil with an aqueous solution of a water-soluble salt of the metal.

The quaternary ammonium salts of the compounds of Formula 1 are prepared by reacting the substituted uracil with an appropriate quaternary ammonium hydroxide. Since these hydroxides are generally available in solution, the reaction is most conveniently carried out in the same solvent. If the solvent-free salt is-desired, it can be easily prepared by removing the solvent.

Alternatively, the quaternary ammonium salts of the uracils can be prepared in a dry inert solvent such as toluene or xylene. The appropriate quaternary ammonium halide is then added with stirring and, if necessary, mild heating. The sodium halide which forms is removed by filtration, leaving the quaternary ammonium salt of the uracil in solution. If desired, the solvent-free salt can be prepared by removing the solvent, preferably in vacuo.

The nitrogenous base-addition compounds of Formula 2 are prepared by mixing together equimolar quantities of an appropriate uracil and a nitrogenous base. The mixture is gradually heated, with stirring, until a clear melt is formed. On cooling, the addition compound crystallizes. This product can then be recrystallized from a solvent such as benzene, cyclohexane, nitromethane or acetonitrile.

It is sometimes advantageous to use an inert solvent medium to carry out the reaction. Such a solvent moderates the reaction by acting as a heat sink, and allows better control of the reaction, especially if it is being carried out on a large scale. Suitable inert solvents are benzene, cyclohexane, nitromethane, acetonitrile and dioxane.

When an inert solvent is used, the addition compounds are prepared by dissolving the amine in the solvent and then adding the uracil gradually, with stirring. Stirring is continued for from ten minutes to two hours. Mild heating may be necessary. Some addition compounds precipit-ate and can be removed by filtration. Other addition compounds are isolated by evaporating the solvent. The addition compounds prepared in this way are suitable for use without further purification, but can be purified by recrystallization if desired.

In some instances, the uracil and amine are highly soluble in the inert solvent, but the addition compound is not, and so it can be filtered off pure when the reaction is complete.

The complexes of Formula 3 are formed by comelting 9 the uracil and phenol in a 1:1 to 2:1 (uracil:phenol) ratio. They can also be formed by codissolving the reactants, in the same ratio, in a nonpolar solvent such as nitromethane or a mixture of nitromethane and cyclohexane. Process conditions and isolation procedures are the same as those described above for the addition compounds.

HERBICIDAL COMPOSITIONS The uracil compounds in Formulate 1 through 4'can be prepared for use by incorporating them with adjuvants.

The amount of herbicide in such prepartions can vary over a wide range according to need. Generally speaking, they will contain from about 0.5 to 95%, by weight of a uracil.

. Powder and dust preparations can be made by mixing uracils of the invention with finely-divided solids such as talcs, natural clays, pyrophillite, diatomaceous earth; flours such as walnut shell, wheat, redwood, soya bean and cotton seed; or inorganic substances such as magnesium carbonate, calcium carbonate, calcium phosphate, sulfur and lime. These preparations are made by thoroughly blending the active ingredient and the solid. The particles in such preparations are preferably less than 50 microns in average diameter.

Water-soluble preparations can be prepared by mixing a uracil with an alkaline solubilizing agent. Solid bases having a pH of at least 9.5 in a 1% aqueous solution, such as sodium or potassium phosphates, silicates, carbonates, borates, oxides or hydroxides, are suitable. The preparations can contain from 0.5 to 80% active ingredient and from 5 to 99.5% of the solubilizing agent.

Granules and pellets can be made by mixing a finelydivided uracil with a suitable clay, moistening this mixture with from 15 to 20% by weight of water, and then extruding the mass through a suitable die under pressure. The extrusions are cut into pre-determined lengths and then dried. These pellets can be granulated if desired.

Granules or pellets can also be prepared by spraying a suspension or solution of a uracil onto the surface of a preformed granule of clay, vermiculite or other suitable granular material. If the uracil is in solution, it will penetrate into the pores of the granule and so will adhere without the aid of a binding agent. When the active material is insoluble in the liquid and is carried as a suspension, it is preferable that a binding agent such as goulac, dextrin, swollen starch, glue or polyvinyl alcohol be added. In either case, the granule is then dried and ready for use.

The uracils can also be prepared in non-aqueous liquids. Aliphatic and aromatic hydrocarbons, especially those derived from petroleum and having boiling points of from 125 C. to 400 C. are preferred. Hydrocarbons having lower boiling points should not be used because of their undesirable volatilization characteristics and inflammability. These liquid preparations are made by milling the components in a mill such as a pebble mill until the particles have average diameters of from 1 to 50 microns, preferably 5 to 20 microns.

The herbicidal preparations, whatever physical form they take, can also contain a surface-active agent. The surfactant renders the preparations readily dispersible in liquids and improves their action on waxy leaves and the like. For general application, surface-active agents are used in the preparations at concentrations of from about 1 to by weight. Levels of from 0.5 to 6 parts of surfactant for each part of uracil, however, give unusual and unexpected results. Preparations having these higher levels of surfactants show greater herbicidal elfectiveness than can be expected from a consideration of activity of the components used separately.

The term surface-active agent is intended to include wetting agents, dispersing agents, suspending agents and emulsifying agents. Surface-active agents suitable for use are set forth in Detergents and Emulsifiers Up-tm 10 Date, 1962, John W. McCutcheon, Inc, Morristown, NJ. Other surface-active agents which can be used in these preparations are listed in U.S. Patents 2,139,276; 2,412,510; 2,426,417; 2,655,447; and Bulletin 13-607 of the Bureau of Entomology and Plant Quarantine of the U.S. Department of Agriculture.

The preparations can also optionally contain adhesives such as gelatin, blood albumin and such resins as rosin alkyd resins. These increase retention and tenacity of de posits following application.

The salts of the compounds of Formula I are especially advantageous for use as herbicides because they are soluble in Water and can be applied as aqueous solutrons.

With respect to the nitrogenous base-addition comfounds of Formula 2, it has been found that preparation with polar low-molecular weight amines, such as ethanolamines, propanolamines and but-anolamines gives addition compounds soluble in water, especially When the amine is present in excess. Other amines, such as piperidine and octanolamines give addition compounds which are soluble in both water (with an excess of amine present) and hydrocarbon solvents. At the other end of the scale, amines such as dodecylamines, cocoaamines and tallowarnines give the addition compounds high hydrocarbon solubility.

Thus, it is apparent that by properly selecting an amine and forming an addition compound with it, uracils of Formula 2 can be formulated as aqueous solutions, wettable powders, or as an oil-emulsifiable or oil-extendable formulations. In this way, the nitrogenous base-addition compounds give formulation and application advantages, while still maintaining the destribed herbicidal characteristics of the parent uracils.

FORMULATION WITH OTHER HERBICIDES The herbicidal compositions of this invention can be formulated to contain two or more of the uracils. They can also be formulated to contaen other known herbicides in addition to the uracils to give compositions which have advantages over the individual components.

Among the known henbicides which can be combined with the uracils of Formula 1 are:

Substituted areas These urea's can be mixed with the uracils of this invention in proportions of from 1:4 to 4:1, respectively the preferred natio being 1:2 to 2:1.

Substituted triazines 2-chloro-4,6-bis (ethylarnino -s-triaz-ine 2-chloro-4-ethylamino-6-isopropylaminoas-triazine 2-chloro-4,6-*bis (methoxypropylamino -s-triazine 2-meth=oxy-4, b-is isopropylamino -s-triazine 2-diethylaminor4-isopropylacetamido-6-methoxy-striazine 2-isopropylamino-4-methoxyethylamino-6-methylrnercaptos-tri'azine 2-rnethyhnercapt-o-4,6-bis( isopropyl-amino)-s-triazine 2-methylmercapto-4,6-bis(ethylamino)-s-triazine 2-methylmercapto-4-ethylamino-6-isopropylarnino-striazine 2-rnethoxy-4,6-b-is (ethylarnino) -s-triazine 1 1 2-methoxy-4-ethylamino-'6-isopropyl amino-s-triazine 2-chloro-4,6bis(isopropylamino)-s-triazine These triazines can be mixed with the uracils of this invention in proportions of from 1:4 to 4:1, respectively, the preferred ratio being 1:2 to 2: 1.

Phenols Dinitro-o-sec-butylphenol and its salts Pentachlorophenol and its salts These phenols can be mixed with the uracils of this invention in the proportions of 1:10 to 20:1, respectively, the preferred ratio being 1:5 to 5: 1.

Carboxylic acids and derivatives The following carboxylic acids and derivatives can be mixed with the uracils of this invention in the listed proportions:

Mixed in a 1:16 to 8:1 ratio, preferably a 1:4 to 4:1 ratio.

2 ,6-d-ichlorobenzonitrile Mixed in a 1:4 to 4:1 ratio, preferably a 1:3 to 3:1 ratio.

Trichloroacet-ic acid and its salts Mixed in a 1:2 to 25:1 ratio, preferably a 1:1 to 8:1

ratio.

2,2-dichloropropionic acid and its salts Mixed in a 1:4 to 8:1 ratio, preferably a 1:2 to 4:1

ratio.

N,N-di(n-propyl)thiolcarbamic acid, ethyl ester N,N-di(n-propyl)thiolcarbamic acid, n-propyl ester N-ethyl-N-(n-butyl)thiolcarbamic acid, ethyl ester N-ethyl-N-(n-butyl)thiolcarbamic acid, n-propyl ester Mixed in a 1:2 to 24:1 ratio, preferably a 1:1 to 12:1 ratio.

N-phenylcarbamic acid, isopropyl ester N-(m-chlorophenyDcarbarnic acid, isopropyl ester N-(mchlorophenyl)carbamic acid, 4-chloro-2-butyny1 ester Mixed in .a 122 to 2411 ratio, preferably a 1:1 to 1211 ratio.

2,3, 6-trichloropheny1acetic acid and its salts Mixed in a 1:12 to 8:1 ratio, preferably a 1:4 to 4:1 ratio.

2-chloro-N ,N-diallylacetamide Maleic hydrazide Mixed in a 1:2 to 10:1 ratio, preferably a.1:1 to 5:1 ratio.

Inorganic and mixed inorganic-organic salts The following salts can be mixed with the uracils in the listed proportions:

Calcium propylarsonate Disodium monomethylarsonate Octyl-dodecylammoniummethylarsonate Dimethylarsinic acid Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1

ratio.

Sodium arsenite J Mixed in a 1:5 to 40:1 ratio, preferably a 1:4 to 25:1 ratio.

Lead arsenate Calcium arsenate Mixed in a 150:1 to 600:1 ratio, preferably a :1 to 400:1 ratio.

Sodium tetraborate hydrated, granulated Sodium metaborate Sodium pentaborate Polyborchlorate Unrefined borate ore such as borascu Mixed in a 3:1 to 150011 ratio, preferably a 6:1 to

1000:1 ratio.

Ammonium thiocyanate Mixed in a 1:10 to 20:1 ratio, preferably at 1:5 to 5:1 ratio.

Sodium chlorate Mixed in a 1:1 to 40:1 ratio, preferably a 2:1 to 20:1

ratio.

Ammonium sulfamate Mixed in a 1:1 to 100:1 ratio, preferably a 1:1 to

50:1 ratio. 1

Other organic herbicides These organic herbicides can be mixed with the uracils in the listed proportions:

, 1,1ethylene-2,2-dipyridy1ium cation 1,1-ethylene-4,4'-dipyridylium cation Mixed in a 1:20 to 16:1 ratio, preferably a 1:5 to 5:1 ratio.

3-amino-1,2,4-triazole Mixed in a 1:20 to 20:1 ratio, preferably a 1:5 to 5:1

ratio.

3,6-endoxohexahydrophthalic acid Mixed in a 1:3 to 20:1 ratio, preferably a 1:2 to 10:1 ratio. v Hexachloroacetone Mixed in a 1:2 to 16:1 ratio, preferably at 1:1 to 8:1 ratio.

Diphenylacetonitrile N,N-dimethyl-a,a-diphenylacetamide 13 N,N-di-n-propyI-2,6-dinitro 4-trifluoromethylaniline N,N-di-n-propyl-2,6-dinitro-A-methylaniline,

a Mixed in a 11:10 1 .30: 1- ratio, preferably a1 is to 20.1

ratio. r

14 Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio. 7

All of the foregoing ratios are weight ratios.

EXAMPLES (F) In Order thatthe invention may be better understood, -(2,4-dichlorophenyl)-O-methyl=isopropylphos- I I the examples are glven:

phoramidothiate l a i I Preparation of active ingredients 2,3,5,6-tetrachloroterephthalic acid," diniet-hyl ester I EXAMPLE 1 v 1 I. M a zolxatlo preferably a to Preparation of 3-sec-butyl-6-cycl0butyluracil.-Eight- Ta v G een parts sec-butylurea, 60 parts benzene, 26.5 parts 3- keto-fi-cyclobutone propionic acid, ethyl ester and 1 part 2,4-dichloro-4-nitrodiphenyl.ether p-toluenesulfonic acid are heated under reflux for 24 2,3,S-trichloro-4-pyridinol hours using a Dean-Stark moisture trap. The reaction mix- 4-amin0-3,5,6-trichloropicolinic acid 'ture is cooled and a solution of 5.3 parts sodium meth- A I J V oxide in 35 parts methanol is added. The mixture is heated ig m a 0 9 9:13am. Preferably a to under reflux 45 minutes, then cooled, and poured into 300 "v parts cold water and 100 parts ether. The organic layer Other substituted 'uracils 20 is removed and the aqueous layer washed with ether. These uracils can be mixed with other substituted urawhen aqueus,1ayer ls fj acidic by addmon 9 ens in the propositionslisted below a strong acid, a white crystalline solid separates. ThlS product is collected on a filter, washed with water, and (A) dried. It melts at 166-167.5 C. After recrystallization 3{yewhexyl 6 methymracfl from nitromethane it melts 1705-1715 C. 3 cyc10hexyl 6 ethyluracil By substitution of a molecular equivalent of the ap- 3tcyclohexybsSec buty1urafl propriate B-cycloalkyl-fl-ketopropionic ester the following w dh m fl uracils are prepared in the same way: 3-cyclopentyl 6 methyluracil EXAMPLE 2 3CycloheXy1'51wPmPy1mac1l I 3-sec-butyl-6-cyclopentyluracil, M.P. 207.5-209" C.

Mixed in'a 1:4 to 4:1 ratio, -pre ferably a 1:2 to 2:1 r EXAMPLE 3 F I I 3-sec-butyl-6-cyclopropyluracil,M.P.170-171 C. Y 1 H 5 EXAMPLE 4 '3-cyclohexyl-5,6i-trimethyleneuracil- 3 Preparation of 5-br0m0-3-sec-butyl 6 cyclobutylnra- 3sec-butyl-5-,6-trimethyleneuracil cil.-Eleven parts 3-sec-buty1-6-cyclobutyluracil, 4.2 parts 3 isopropyl'15,6-trirnethyleneuracil.' anhydrous sodium acetate and 70 parts glacial acetic acid 3-isopropyl-5,6-tetrarnethyleneuracil 3 are stirred together at 30 C. while 8.0 parts bromine are 3-isopropyl-5,6-pentamethyleneuracil 40 added dropwise. One hour after the addition is complete, r I l r the solvent is evaporated under reduced pressure, and the M d P p k a a to residue is triturated with water. The White crystalline P m. H r residue is collected on a filter, washed with water, and

(c) dried. The product melts at 156-158 c. I 3-cyclohex l-5-bro'mouracil i In the same'way by substitution of a molecular equivay '?,-cyclohexyl-5-chlorourac1l; lent of the approprlate unhalogenated uracil, the following 3-isopropyl-5?bromouracil uracils are prepared:

l Uracil st artmg Reactant Halogen Uracil Product 6-cyclopropyl-3-methyluracil. Br 5-br0mo-6-cyclopropyl-3-methyluracil.

I 6-cyc1opropyl-3-(2'dodecyDuraciL Br 5-bromo-6-oyclopropyl-3-(2-dodecyDuracil. 6-cyc1oheptyl-S-isbpropylnraeil.-L 1.. Br 5-br0mo-6-cycloheptyl-3-isopropyluracil. g' ,6 cycl0propyl-3-methoxymethyluraciL Br 5-brom0-6-cyclopropy1-3-1nethoxymethyluracil.

* (icyclogentyl-B-(l-naphthybdracil.. C1 5'chloro-6cyelopentyl-3-(l-naphthyl)uracil. 3 -cyclo exyl-S-cyclopropyluraciL. Br 5-bronlo3-cyclohexyl-G-cyclopropyluracil. 3-(2-methylcyclohexyl)-6-eyc1opropyluraci1 Br 5-brorno-3-(2-methylcyclohexyl)-6-cyc1opropyluracil.

3-ter t-buty1-6-cyc1oprppyluraciL Br' 5'bromo:3-tert-butyl-G-cyclopropyluracil.

6-cyclopropyl-3-(l-ethylpropyDuracil.. Br fi-bromo-fi-cyclopropyl-Zi-(l-ethylpropyburacil. 3 tert-butyl-fi-cyclopropyluracil Cl 5-chloro-3-tert-butyLG-cyclopropyluracil.

-: 3sec-buty1-6-cyclopentyluracil-.

3-sec-butyl-5 broh1ouracil v v m 3-sec-butyl-5 chlorouracil Y 1 Mixed in are to 6:1 ratio preferably ia 1:2 to 22.1 I

5-brom0-6cyclopropyl-Zl-phenyluracil. 5-eh10ro-3-(3-chloropheny1)-6 cyclopropyluracil. 5-bromo-3-sec-butyl-fi-cyclopentyluracil. r 5-bron10 3-sec-butyl-G-cyclopropyluracil.

20.8 parts of 3-butyl 6 methyluracil in parts of glacial acetic acid. The temperature is maintained below 30 C.

during this addition; The solution is stirred /2 hour longer at room temperature, then poured into ice water, whereupon'a solid separates. This solid is collected by filtration and washed well with water to give crude 3-butyl-5-chloro- 61cyclopropyluracil. It is then recrystallized from a mixture of cyclohexane and ethyl acetate to give pure 3:butyl=.

5-chloro-6-cyclopropyluracil.

EXAMPLE 6 EXAMPLE 7 Preparation of 3-allyl-fi-cyclopropyl-S-methyluracil.A mixture of 19.6. parts by weight of allylurea, 37.4 parts Uracil Starting Reactant nxizuurms Preparation of 3 sec-[Julyl-6-cyclopenty-l-5-niireuracil.A solution of 40 parts .by volume of fuming nitric acid and 40 parts by volume of fuming sulfuric acid (20% S0 is stirred at 30 C. while 20 parts by Weight of 3 sec-butyl-fi-cyclopentyluracil are added portion-wise over a -minute periodThe solution-is stirred an additional 30 minutes, then poured slowly into A volumes of a stirred ice-Water mixture The uracilseparates out as a pale yellow solid. It is collected by filtration, washed well with water, and air dried. It may be recrystallized to give essentially 3-sec butyl-6-cyclopentyl-5-nitrouracil.

The following S-nitro substituted uracils can be similarly prepared by substituting:equivalent amounts of thesubstituted uracil starting reactants'set forth in the following table for 3-sec-butyl-6-cyclopentyluracil 5-N itrouracil Product 3-tert-butyl-6-cyclopropyluracil 3-cyclohexyl-fi-cyclopropyluracil 3tert-butyl-6cycl0propy1-5-nitrouracil. 3-cyclohexyl-6-cyclopropyl-5 nitrouracil.

3-(3-ch1oro-5methylphcnyl) -6-cyclopropyluracil 3-(3-chl{)ro-5-methylphenyl)-6-cyclopropyl-5-nitro.

uracl 6-cyclobutyl-3-(3-nitrophenyl)uracil 6-cyc1obutyl-5-nitro-3-)3-nitrophenyl)uracil.

3- (3-ch10ro-5-nitrophenyl) -6-cyclopropyluracil 3-(3-chl0ro-5-nitrophenyl) -6-cyelopropyl-5-nitrouraci1.

3-(3-chlor0-4-methoxypheny1) -6-cyclopro pyIuraciL... 3-(3-chliaro-i-methoxyphenyl) -6-cyclopropy1-5-uitrouraci 6-cyclopropyl-3-(3-trifluoromethylphenyl)uracil G-cyclopropyl-S-uitro-3-(3-trifluoromethylphenyl) uracil.

6-cyclopropyl-B-tetrahydronaphthyl 3,6-dicyclo propyluracil (S-cyclopropyl-3-octahydr0-1,4-5;8-dimethanonaphtliyluracil.

6-cyclopr0pyl-5'nitro-3-tetrahydrouaphthyluracii.

3,G-dicycloprooyl-5-nitrouraoil.

o-cyclopropyl-fi-nitro-3-0ctahydro-1,45,8-dimethan0- naphthyluracil. g,

by weight of ethyl 3-cyclopropyl-3-keto-2-rnethylpropionate, 0.5 part by weight of 85% orthophosphoric acid, and 200 parts by weight of benzene is heated at reflux. Water is collected in a Dean-Stark trap. After 24 hours, the solution is cooled, decanted and evaporated to a mixture of viscous oil and solid, which is taken up in 200 parts by weight of ethanol containing 10.6 parts by weight of sodium methoxide and heated at reflux for 10 minutes. Most of the ethanol is removed under reduced pressure and the residue is taken up in just sufficient water to dissolve it. Concentrated hydrochloric acid is added to lower the pH to 4 and the resulting white solid is collected by filtration. The solid is recrystallized from an ethanol-water mixture to give pure 3-allyl-6-cyclopropyl-S-methyluracil.

The following uracils are similarly prepared by substituting equivalent amounts of the ureas and equivalent amounts of the fi-keto ethyl esters set forth in the table EXAMPLE-9 1 Preparation of 3 cyclohexyl-6-cyclopropyl-S-hydroxym ethyluracil.A mixture of 234 parts by weight of 3- cyclohexyl-6-cyclopropyluracil, 1400 parts by weight of water, 315 parts by weight of ethyl alcohol, 66 parts by weight of paraformaldehyde, and ZO'partsby weight of barium hydroxide is heated until the components are completely dissolved. The solution is then stripped and the oil which remains is extracted with ether. This ether extract is dried with magnesium sulfate, filtered, and concentrated at reduced pressure to a slightly gummy solid. This solidis' recrystallized from acetonitrile to give essentially pure 3-cyclohexyl-6-cyclopropyl-5-hydroxymethyluracil.

The following compounds are similarly prepared by substituting equivalent amounts of the designated uracil starting reactants for 3-cyclohexyl-6-cyclopropyluracil:

Uracil Starting Reactant 3'sec-butyl-trcyclopropyluracil 3-tBl't-bllty1-6-CYC1ODTODY1UI80H 3-0yc1obutenyl-6cyclopr0p yluracil 6-cyclobuty1-3-indenyluraeil 6-cyclopropyl-3furfuryluraci1- (rcycloprop ylQ-octenylumcil. eeyclopropyl-Z-propargyluracil 6-allyl-3-octynylurac1l 3-cyclooctyl-(icyclopropyluracil.

'3-cycloheptyl-G-cyclohexyluracil fi'cyclopropyl-3-decahydro-l,4-5,8-dimethanonaphthyluracil.

Uracil Product for the allylurea and ethyl 3-cyclopropyl-3-keto-2-methyl' 5-hydroxymethyluraciL EXAMPLE 10' propionate: Preparation of 3-is0pr0pyl-5-chl0r0m12thyl-6-Cycl0hexflJietoestr Substituted Urea Uracil Product B-cyclopropy1-3-keto-2-mcthylpropionate 3-sec.butylurea 3-sec-butyi-6-cycloptopylefi-methyluracil.

D0- B-tert-butylurea S-tert-butyl-ficyclopropyl-S methyluracil.

. 3-cycl0hexylurea. (3-bromophenyl)urea.

(4-ethoxypheny1) urea 3-cyclopropyl-3-keto-Z-methoxypropionate. (2-flu0rophenyDurea 6-cycl0 ropyl- (2-fluor0phenyD-B-methoxyuracil. 3-cyclobutyl-3-keto-2-butoxyprop1onate. (3,5-dibromophenyDurea trcyclo utyl3-(3,51dibromophenyl)-5-butoxyuracil. 3-cyclopentyl-Z-ethoxy-3-kctopropionate. (2,4,5-trichlorophenyl)urea ficyclopentyl-Zi-(2,4,5-trichlorophenyl)'5-ethoxyuracil. 3-cyclohexyl-3-ketc-2-propoxypropionate. (3tolyl)urea fi-cyclohexy1-3-(3-tolyl)-5-propoxyurac' 3-(4-ethylnaphthyDurea 3-cyclopropylmethylurea l-octahydro-l,4,5,8-dimethanonaphthylmethyl dimethanonaphthylmathyDuracil.

17" yluracil.A mixture of 22 parts by weight of 3-isopropyl- 6-cyclohexyluracil and 38 parts by weight of chloromethylmethylether is heated in an autoclave under endogenous pressure at 100 C. for 25 hours. The material is cooled and the excess reagent evaporated under vacuumfThe product is extracted from the residue with dry dioxane. The dioxane is then evaporated to dryness, leaving essentially pure 5-chloromethyl-3-isopropyl-6-cyclohexyluracil as a residue.

EXAMPLE 11 Preparation of 6 cyclopropyl-S-dhl0r0m-ethyl-3-iso-pr0- pyluraciL-To 452 parts of rapidly stirred thionyl chloride, maintained below 25 C. with an ice bath, are gradually added 224 parts of 6-cyclopropyl-5-hydroxymethyl- 3-isopropyluracil. Caution should be used in carrying out this reaction because of the large amounts of acidic gases produced and the vigor of the reaction.

a An eflicient condenser is used to retain the thionyl chloride reactant, and a scrubber is used to wash away the gases produced.

When a complete solution has been obtained, it is distilled to dryness at reduced pressure at 50 C. The solid is triturated with 2 00 parts of a 1:1 mixture of 1,1,2-trichloroethane and heptane, and filtered.

The solid is then recrystallized from 600 .parts of the same solvent, giving essentially pure 6-cyc1opropyl-5- chloromethyl-3 -isopropyluracil.

The following S-halomethyluracils can be prepared by the method of Example 11 by substituting an appropriate thionyl halide and substituted uracil for the thionyl chloride and S-hydroxymethyl-3-isopropyl-6-cyclopropyluracil of Example 11: l

The dry filter'cake is recrystallized. from acetonitrile to give pure 5-chloro-6-chloromethyl-3-isopropyluracil.

A solution of 7 parts of sodium methylmercaptide in 250 parts of methanol is prepared. To this mixture is added 23.7 parts of 5-chloro-6-chloromethyl-3-isopropyluracil. The resulting mixture is boiled under reflux for 4 hours, cooled, and the solvent removed under vacuum.

After washing the residue with water, the material which.

EXAMPLE 15 Preparation of 3 cyclohexyl 5 -.(2 hydr0xyethyl)-6- cyclopropyluracil.-A mixture of 426 parts by Weight of cyclohexylurea, 43.l parts by Weight of 2-keto-3-cyclopropylcarbonyltet-rahydrofuran' (which is prepared from 3-l eto-3-cyclopropylpropionic acid, methyl ester, and ethylene oxide by known methods), 879 parts by weight of benzene, 1030 parts by weight of dioxane, and 40 parts by weight of 85% phosphoric acid is stirred at reflux temperature.

The water given off is removed by azeotropic dis'-' tillation. When no more water is given off, the solution is' cooled, decanted, and concentrated to dryness under reduced pressure. Three recrystallizations of the resulting Uracil Ihionyl Halide I Product 3-(2-chlorocyclobutyl)-5 hydr0xymethyl-6, cyclo- Thionyl bromide .3-(2-chl0rocyelobutyl)-5-bromomethyl-6-eyclo-- pentyluracil. pentyluracll. I

EXAMPLE 12 solid from acetonitrile give 3-cyclopropyl-3-(3-cyclo Prepamlion of 6 cyclopropyl-3-isopropyl-5-rireihoxymethyluracil.To a warm solution of 23.5 parts by weight of 5-chloromethyl-3-isopropyl-6-cyclopropyl-uracil in 150- 200 parts by weight of methanol is added 5.4 parts by weight of sodium methoxide. The solution is heated to reflux for 15 minutes. The methanol is then evaporated, and the product extracted with ether. Evaporation of the ether yields 3-isopropyl-S-methoxymethyl-6-cyclopropyluracil in a crystalline state.

I EXAMPLE .13

Preparation of 3-z's0pr0pyl-5-methylthi0methyl-6-cycloheptyluracil.-A suspension of 30.1 parts by Weight of 5-.chloromethyl-$-isopropyl-fi-methyluracil and 7.0 parts by weight of sodium methylrnercaptide in 100 parts by weight of tetrahydrofuran is heated to refiux for minutes while gaseous methylmercaptan is added at a slow rate. The solvent is then evaporated and the product extracted from the residue with ether. Evaporation of the ether yields the desired 3-isopropyl-S-methylthiomethyl- G-cycloheptylu-racil in a crystalline state.

EXAMPLE :14

Preparation of 5 chl0r0-6-m-ethylthiomethyl-3-isopropyluracil.--A mixture of 168 parts of 3-isopropyl-6-methyluracil, 100 parts of acetic acid and 650 parts of water is vigorously stirred as 147 parts of chlorine are gradually added as a gas. The temperature is maintained at 30' C. to 35 C. with a cooling bath.

The white slurry is stirred for an additional hour and 400 parts of concentrated hydrochloric acid are then added gradually With stirring. The slurry is heated at reflux for 5 hours, chilled to about 20 C. and filtered. The filter cake is resuspended in 500 parts of cold water and refiltered.

hexylureido)-2-(2-hydroxyethyl) acrylic acid, 'y-lactone.

' A mixture of 302 parts by'weight of the 3-.cyclop'ropyl- (3-cyclohexylureido)-2-(2-hydroxyethyl)acrylic acid, ylactone, 1580 parts by Weight of absolute ethanol, and 130' parts by Weight of sodium methoxide is refluxed for 15 minutes. It is then concentrated to dryness atreduced pressure, and the residue is dissolved in 1500 parts 'by Weight of water.

This solution is cooled, acidified with hydrochloric acid to pH 5, and the resulting White precipitate, 3-cyclohexyl- 5-(2-hydroxyethyl)-6-cyclopropyluracil, is filtered, off, dried, andrec-rystallized from a mixture of ethanol and water. l

' EXAMPLE 16 Preparation of 3-bittyl-S-chloro-6-zillyluracil, sodium salt.A solution of 4 parts of sodium hydroxide in lOQ parts of water is treated with 24.6 parts of 3-butyl 5- chloro-6-methyluracil. Stir-ring and warming is employed to effect solution. The Water is removed from the solution under reduced pressure, leaving 3-butyl-5-chloro-6 allyluracil, sodium salt, as a white solid.

The metal salts of the compounds prepared according to the foregoing examples can be prepared as in Example 16 by substituting equivalent amounts of other substituted uracils and other hydroxides for the 3-butyl-5- chloro-6-allyluracil and sodium hydroxide. The following list contains examples of salts prepared in this fashion:

3-sec-butyl-5-chloro-6- (2-butenyl)uracil, sodium salt 3-butyl-5-iodo-6-cyclobutyluracil, potassium salt 3-phenyl-5-methoxy-6-cyclopropyluracil, tetramethylammonium salt B-(m-fluorophenyl)-5-bromo-6-methylthiouracil, /2

magnesium salt 1 9 3- 3 a,4,5,6,7,7a-hexahydro-4,7-methano-S-indanyl) 5-bromo-6-allyluracil, sodium salt EXAMPLE 17 Preparation of 1 :1 complex of 5-bromo-3-isoptropyl-6- cyclobutyluracil and pentachlorophenol.-A mixture of 29.1 par-ts of 5-br0mo-3-isopropyl-6-cyclobutyluracil, 266 parts of pentachlorophenol and 1250 parts of cyclohexane is stirred at reflux as 50 parts of nitromethane are gra=dually added. The physical appearance of the solid changes rapidly. When no further change is noticed, the mixture is chilled and the solid product is filtered off and recrystallized from nitromethane.

. The following complexes can be prepared in a similar fashion by substituting equivalent amounts of the proper phenol and uracil for the 5-bromo-3-isopropyl-6-cyclobutyluracil and pentachlorophenol:

1:1 complex m-methylphenol and 5-bromo-3-sec-butyl- 6-methylthiouracil 1:1 complex p-nitrophenol and 5-bromo-3-sec-butyl-6- butoxy-methyluracil 1:1 complex phenol and 3-isopropyl-5-methyl-6- cyclopentyluracil EXAMPLE 18 Preparation of the ethanolamine addition compound -br0mo-3-isopr0pyl-6-cyclobutylaracil.A solution is prepared by mixing together 283 parts of 5-bromo-3- isopropyl-G-methylu-racil, 392 parts of acetonitrile and 61 parts of ethanolamine. The solvent is distilled oif at reduced pressure and the oil which remains gradually solidifies. The molar addition compound is recrystallized from nitromethane.

EXAMPLE 19 Percent 3-cyclohexyl-6-cyclopropyluracil, sodium salt 20 Sodium lauryl sulfate 2 Water 78 The solution is prepared by dissolving the two soluble salts in the water, with agitation. The solution is suitable for quick dilution to desired spray levels.

Other soluble salts suitable for preparation of water concentrates are 3 sec-butyl-S-bromo-6-cyclopropyluracil, sodium salt 3-isopropyl 5 chloro 6 cyclopropyluracil, tetrabutylammonium salt This aqueous solution is used for post-emergence weed control. A concentration of 1.0 pound of active ingredient per acre in 30 gallons of water gives excellent control of crab grass, pigweed, velvet Weed, and fiower-of-an-hour.

At concentrations of to pounds per acre in 80 gallons of water, this composition gives excellent control of a wide variety of annual and broadleaf weeds growing in railroad yards on railroad ballast.

EXAMPLE 21 Percent 5-bromo-6-cyclopropyl-3-isopropyluracil 50 Ethanolamine T, s s, 50

The components are mixed together at room temperature until a clear solution is formed. This solution is infinitely extendable with water and can be diluted to any concentration.

Ten pounds of this formulation are mixed with 60 gallons of water in a spray tank. Ten pounds of trimethylnonyl ether of polyethylene glycol, are added. Only slight agitation is required for complete mixing.

Sixty gallons of this solution are applied to an acre of roadside. Excellent initial kill of foliage and residual weed control is obtained. Such species as wild oats, cheatgrass, crab grass, foxtails, ryegrass, volunteer small grain and wild mustard are controlled.

Oil formulations EXAMPLE 22 Percent 3-cycl0hexyl-5-bromo-6-cyclopropyluracil 25 Blend of polyalcohol carboxylic esters and oil-soluble petroleum sulfonates Diesel oil 69 These components are mixed together and milled in a roller mill, pebble mill, or sand mill until the particles of the active component are substantially all below 10 microns in size. The resulting suspension can be emulsified in water or diluted further with weed oils for spray application.

This formulation is diluted with gallons of Lion Herbicida'l Oil--No. 6 and applied at 10 to 20 pounds of active ingredient per acre for the control of weeds such as morning glory, chickweed, pigweed, lambs quarter, yarrow, ragweed, wild carrot, quack grass, witch grass, crab grass, and oak and maple seedlings growing along railroad rights-of-way. Excellent control is obtained.

EXAMPLE 23 Ten pounds of 3-sec-butyl-5-bromo-6-cyclopentyluracil as an 80% wettable powder and 2 pounds of 4,6-dinitroortho-secondary butylphenol in 4 gallons of oil are blanded as a tank mix and applied at 12 pounds of active herbicide per acre in gallons of Water to weeds growing along fence rows. Quick kin of annual and perennial broadleaf and grass weeds is obtained, with excellent residual weed control.

EXAMPLE 24 Percent 3-sec-butyl-5-chloro-6-cyclopropyluracil, Na salt 25 Granular 8-15 mesh attapulgate clay 75 A granular composition is prepared by dissolving the active ingredient in water and spraying this solution on the :attapulgite granules while they are tumbled. The reresulting granules are then dried.

The granules are applied by hand for spot treatment of undesirable bunch grasses growing in agricultural areas. An application of 20 to 30 pounds of active ingredient per acre gives good control of Dallis and vasey grass.

EXAMPLE 25 Percent 3-tert-butyl-5-chloro-6-cyolopropyluracil 3.3 3-phenyl-1,l-dimethylurea 6.7 California Ca, Mg sub-bentonite 75.0 Anhydrous sodium sulfate 15.0

This composition is blended, micropulverized, pugmilled with about 20% water, moist-granulated and then dried. It is then screened to give 15-30 mesh granules.

Applied at 15 pounds of active ingredient per acre, these granules give excellent control of such weeds as bitterweed, partridge pea, beggars-lice, ragweed, crab grass, cheat, and common lespedeza, growing along guard rails and around sign boards.

21 EXAMPLE 26 Percent 3-isopropyl-5-chloro-6 methoxyrnethyluracifl 2.0 Sodium chlorate 38.4 Sodium borate 59.6

A mixture of the-crystalline chlorate and borate is placed in a blender. Finely ground uracil is slurried in water and sprayed on the chlorate-borate mixture While it is blended.

This formulation is effective against grass and broadleaf weed infestations, and can be easily applied on railroad rights-of-way. An application of 400 pounds per acre of these granules gives outstanding control of little bluestem, broomsedge, foxtail, crab grass, ragweed, pigweed, henbit, and knotweed.

Soluble powders EXAMPLE "27 This formulation is prepared by blending, micropulverizing and then reblending the following ingredients:

Percent 3-isopropyl-5-bromo-6-cyclopentyluracil Sodium metaborate 40 Dioctylsodium sulfos-uccinate Sodium lignin sulfonate 2 Finely-divided synthetic silica 8 The active ingredient in this formulation is soluble in water when the formulation is added to Water to make a 4% concentration.

One hundred .gallons of a 4% concentration of this formulation are applied to an area of one acre in a sawmill yard infested with annual weeds. Outstanding control of crab grass, foxtail, ragweed, barnyard grass, bromegrass and pigweed is obtained.

Wettable powders EXAMPLE 28 This formulation is applied in 100 gallons of Water, at 20 pounds of active ingredient per acre, for the control of finger grass, foxtail, lovegrass, nut-grass, vasey grass, broomsedge, sand spur, goldenrod, ragweed, beggar-tick, and spurge growing around oil tanks. The formulation gives a good rapid kill of foliage and has long-lasting residual activity in the soil.

Two pounds (active) of this formulation is dispersed in gallons of water. When applied premergence or early post-emergence to the tender weeds, excellent control of annual grasses and broadleaf weeds growing in sugar cane is obtained. A post-emergence spray, directed under the cane plants, gives good control of rice grass, crab grass, goosegrass, seedling Johnson grass, Ageratum, pigweed, lambs quarters and velvet leaf.

The invention claimed is:

1. A method for the control of undesirable vegetation, said method comprising applying to a locus to be protected at herbicidally effective amount of a compound of the formula 22 where R is selected from the group consisting of alkyl of 1 through 10 carbon atoms,

substituted alkyl of 1 through 8 carbon atoms, wherein said substitutent is selected from the I group consisting of bromine, chlorine, hydroxy,

alkoxy, alkoxycarbonyl, and cyano,

- aryl of 5 through 10 carbon atoms,

substituted phenyl, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, alkoxy of 1. through 5 carbon atoms, alkyl of 1 through 6 carbon atoms, nitro, trifiuoromethyl, 1,2-tetramethylene, and 1,2-trimethylenylene,

aralkyl of 5 through 13 carbon atoms,

substituted aralkyl of- S through 13 carbon atoms, wherein said substitutent is selected from the group consisting of chlorine, nitro, alkyl, and alkoxy,

tetrahydronaphthylalkyl,

alkenyl of 3 through 8 carbon atoms,

alkynyl of 3 through 8 carbon atoms,

cycloalkyl of 3 through 12 carbon atoms,

substituted cycloalkyl of 3 through 12 carbon atoms, wherein said substitutent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl,

cyoloalkenyl of 4 through 12 carbon atoms, substituted cycloalkenyl of 4 through 12 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoXy, and alkyl,

cycloalkyl alkyl of 4 through 113 carbon atoms,

cycloalkenyl alkyl of 5 through 13 carbon atoms,

(substituted cycloalkyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl, and

(substituted cycloalkenyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl;

R is selected from the group consisting of chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoXy, nitro, alkoxyrnethyl of 2 through 6 carbon atoms, hydroxy alkyl of 1 through 2 carbon atoms, alkylthio containing 1 through 4 carbon atoms, bromomethyl, fluoromethyl, and chloromethyl;

R is selected from the group consisting of cycloalkyl of 3 through 7 carbon atoms, alkenyl of 3 through 5 carbon atoms, alkylthio of 1 through 4 carbon atoms, alkylthiomethyl of 2 through 3 carbon atoms, and alkoxymethyl of 2 through 5 carbon atoms; with the further proviso for said formula that when R is cycloalkyl of 3 through 7 carbon atoms, R can be hydrogen.

2. A method for the control of undesirable vegetation, said method comprising applying to a locus to be protected a herbicidally effective amount of a compound of the formula where R is selected from the group consisting of alkyl of 2 through 8 carbon atoms, substituted alkyl of 2 through 8 carbon atoms wherein said substituent is selected from the 23 24 group consisting of bromine, chlorine, hydroxy, bon atoms, wherein said substituent is selected alkoxy, alkoxycarbonyl, and cyano, from the group consisting of bromine, chlorine, phenyl, methoxy, and alkyl; substituted phenyl, wherein said substituent is se- R is selected from the group consisting of lected from the group consisting of chlorine, 5 chlorine, bromine, iodine, methyl, 'hydroxymethyl, bromine, fluorine, alkoxy of 1 through 5 carbon methoxyrnethyl and hitro; and atoms, alkyl of 1 through 6 carbon atoms, nitro, R is selected from the group consisting of trifluoromethyl, 1,2-tetramethylene, and 1,2-trialkoxymethyl of 2 through 3 carbon atoms, cyclomethylenylene, alkyl of 3 through 6 carbon atoms, and alkenyl aralkyl of 6 through 10 carbon atoms, 10 of 3 through 4 carbon atoms. substituted aralkyl of -6 through 10 carbon atoms,

wherein said substituent is selected from the Rfifel'ellces Cited group consisting of chlorine, nitro, alkyl, and UNIT D STATES P N S alkoxy, cycloalkyl of 3 through 8 carbon atoms, 5 3235357 2/1966 Loux 260 260 cycloalkenyl 5 thmugh 8 JAMES 0. THOMAS, JR., Primary Examiner cycloalkyl alkyl of 4 through 9 carbon atoms, or (substituted cycloalkyl)alkyl of 5 through 10 car- LEWIS GOTTS: Exammer- 

1. A METHOD FOR THE CONTROL OF UNDESIRABLE VEGETATION, SAID METHOD COMPRISING APPLYING TO A LOCUS TO BE PROTECTED A HERBICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OF THE FORMULA 